JPH11181075A - Isolation of polyhydroxycarboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for isolating a formed polyhydroxycarboxylic acid in a satisfactory form with respect to quality and productivity. SOLUTION: A hydroxycarboxylic acid and/or its oligomer is treated with a haloiminium salt to give a solution of a polyhydroxycarboxylic acid. A reaction solvent/a solvent different from the reaction solvent is removed under reduced pressure while dripping the solution into water/the solvent different from the reaction solvent to give a water slurry solution, which is filtered, washed and dried to isolate the objective polyhydroxycarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a biodegradable polyhydroxycarboxylic acid as a substitute for a medical material and a general-purpose resin, and to a method for isolating a polyhydroxycarboxylic acid obtained by using a haloiminium salt.

[0002]

2. Description of the Related Art Polyhydroxycarboxylic acids have excellent mechanical, physical and chemical properties, and are decomposed in a natural environment without causing any harm. It has a biodegradable function of becoming carbon dioxide gas, and has been attracting attention in various fields such as medical materials and alternatives to general-purpose resins in recent years, and its demand is expected to increase significantly in the future. In particular, when recycling becomes mandatory for existing general-purpose resin products, it is expected that replacement with biodegradable polymers will progress, and beverages,
Demand is expected to increase for applications such as detergents, various containers for cosmetics, storage cases for clothes and miscellaneous goods, food packaging materials, and films for coating.

[0003] As a conventional method for producing polyhydroxycarboxylic acid, a method is disclosed in which a lactide is synthesized from a cyclic dimer of a monomer, for example, lactic acid, purified, and then subjected to ring-opening polymerization in the presence of a catalyst (US Pat. 703, 316 etc.)
It has been known. Further, a method of directly dehydrating lactic acid in the presence of a catalyst to carry out polycondensation (JP-A-59-96123,
U.S. Pat. No. 4,273,920) is known. In recent years, a method of obtaining a polyhydroxycarboxylic acid by performing a polymerization by reacting a haloiminium salt with a hydroxycarboxylic acid has been found (EP0766912). This method comprises a reaction in which a carboxyl group of a hydroxycarboxylic acid is halogenated with a haloiminium salt to form an acid halide, and a subsequent reaction between the acid halide and a hydroxyl group. Thereby, it has become possible to easily obtain polyhydroxycarboxylic acid by a simple operation as compared with the above method.

In the case of carrying out polymerization using a haloiminium salt, amides, ureas and imidazolidinones formed after the haloiminium salt reacts are mixed in the reaction solution. If the compound remains in the polymer, the color tone may deteriorate during the heat treatment in the processing stage.
Therefore, it is desirable to separate the compound to isolate the polyhydroxycarboxylic acid. As a separation method generally considered, there are a method of volatilizing the compound from the reaction solution and a method of removing the compound by precipitating and washing a polymer.
However, when the reaction solution is concentrated to volatilize and remove the compound, many of the compounds have a high boiling point, so that the concentration conditions are also high and the color tone may be deteriorated during the treatment. In addition, when the polymer is precipitated and isolated, the yield may be reduced.

[0005]

As described above, in the case of carrying out polymerization using a haloiminium salt, a method for isolating the produced polyhydroxycarboxylic acid in a satisfactory manner in terms of quality and productivity is established. Was required. The present invention seeks to solve this problem.

[0006]

Means for Solving the Problems The present inventors have developed a method for isolating the produced polyhydroxycarboxylic acid in a satisfactory manner in terms of quality and productivity when performing polymerization using a haloiminium salt. We made it a subject to provide, and examined it diligently. As a result, surprisingly, while mixing the polymerization reaction solution obtained by polymerization using the haloiminium salt with a suspension of a solvent different from the reaction solvent and water, or after mixing, the reaction solvent and the reaction solvent are By distilling off different solvents and precipitating polyhydroxycarboxylic acid in water, and then performing solid-liquid separation of the slurry, it is possible to isolate polyhydroxycarboxylic acid satisfactorily in terms of yield, quality and productivity. The inventors have found and completed the present invention.

That is, the present inventors mixed a solution of polyhydroxycarboxylic acid obtained by reacting a hydroxycarboxylic acid and / or an oligomer thereof with a haloiminium salt with a suspension of water and a solvent different from the reaction solvent. The polyhydroxycarboxylic acid is characterized in that the solvent is distilled off while or after mixing, and the polyhydroxycarboxylic acid is precipitated in water, and then the slurry is subjected to solid-liquid separation to isolate the polyhydroxycarboxylic acid. This is a method for isolating an acid.

The following are specific examples of the hydroxycarboxylic acid used in the present invention. Glycolic acid, lactic acid, 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 2-hydroxycaproic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2-hydroxy-2-methylpropionic acid, 2-hydroxy-2- Methyl butyric acid, 2-hydroxy-2-ethyl butyric acid, 2-hydroxy-2-methyl valeric acid, 2-hydroxy-2-ethyl valeric acid, 2-hydroxy-2-propyl valeric acid, 2-hydroxy-2-methyl caproic acid Acid, 2-
Hydroxy-2-ethylcaproic acid, 2-hydroxy-
2-propylcaproic acid, 2-hydroxy-2-butylcaproic acid, 2-hydroxy-2-methylheptanoic acid,
2-hydroxy-2-ethylheptanoic acid, 2-hydroxy-2-propylheptanoic acid, 2-hydroxy-2-butylheptanoic acid, 2-hydroxy-2-pentylheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxy-2-ethyloctanoic acid, 2-hydroxy-2
-Propyloctanoic acid, 2-hydroxy-2-butyloctanoic acid, 2-hydroxy-2-pentyloctanoic acid,
2-hydroxy-2-hexyloctanoic acid, 2-hydroxy-2-hexylnonanoic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxycaproic acid, 3-hydroxyheptanoic acid, 3- Hydroxyoctanoic acid, 3-hydroxy-3
-Methylbutyric acid, 3-hydroxy-3-methylvaleric acid, 3-hydroxy-3-ethylvaleric acid, 3-hydroxy-3-methylcaproic acid, 3-hydroxy-3-
Ethylcaproic acid, 3-hydroxy-3-propylcaproic acid, 3-hydroxy-3-methylheptanoic acid, 3-
3-hydroxy-3 hydroxy-3-ethylheptanoic acid
-Propylheptanoic acid, 3-hydroxy-3-butylheptanoic acid, 3-hydroxy-3-methyloctanoic acid, 3
-Hydroxy-3-ethyloctanoic acid, 3-hydroxy-3-propyloctanoic acid, 3-hydroxy-3-butyloctanoic acid, 3-hydroxy-3-pentyloctanoic acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid,
4-hydroxycaproic acid, 4-hydroxyheptanoic acid, 4-hydroxyoctanoic acid, 4-hydroxy-4-
Methyl valeric acid, 4-hydroxy-4-methylcaproic acid, 4-hydroxy-4-ethylcaproic acid, 4-hydroxy-4-methylheptanoic acid, 4-hydroxy-4
-Ethylheptanoic acid, 4-hydroxy-4-propylheptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4
-Hydroxy-4-ethyloctanoic acid, 4-hydroxy-4-propyloctanoic acid, 4-hydroxy-4-butyloctanoic acid, 5-hydroxyvaleric acid, 5-hydroxycaproic acid, 5-hydroxyheptanoic acid, 5-hydroxy Octanoic acid, 5-hydroxy-5-methylcaproic acid, 5-hydroxy-5-methylheptanoic acid, 5-hydroxy-5-ethylheptanoic acid, 5-hydroxy-5
-Methyloctanoic acid, 5-hydroxy-5-ethyloctanoic acid, 5-hydroxy-5-propyloctanoic acid, 6
-Hydroxycaproic acid, 6-hydroxyheptanoic acid,
6-hydroxyoctanoic acid, 6-hydroxy-6-methylheptanoic acid, 6-hydroxy-6-methyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7- It is an aliphatic hydroxycarboxylic acid such as hydroxy-7-methyloctanoic acid or 8-hydroxyoctanoic acid and / or an oligomer thereof, and one or a mixture of two or more thereof may be used. In addition, these hydroxycarboxylic acids and their oligomers have an optical carbon, and each has a D
It may take the form of a body, L-form or D / L-form, but in the method of the present invention, the form is not limited at all. These may be used alone or in combination of two or more. Particularly preferably used hydroxycarboxylic acids are lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, or a mixture thereof.

In the method of the present invention, an oligomer derived from the aforementioned hydroxycarboxylic acid can be used as a raw material. The method for producing the oligomer may be a method in which hydroxycarboxylic acid is simply dehydrated by heating under a nitrogen atmosphere, and the average molecular weight of the oligomer may be any. There is no particular limitation on the method.

The haloiminium salt used in the present invention is:
The following formula (1)

Embedded image (Wherein X ₁ and X ₂ each represent a halogen atom and may be the same or different). The compound contains the structure represented by the following formula in the molecule. Also,
There is no problem as long as the compound has the above structure.
Common haloiminium salts include N, N-dimethylchloromethyleneiminium chloride, N, N-diphenylchlorophenylmethyleneiminium chloride,
N, N-diphenylchloro-p-methoxyphenylmethyleneiminium chloride, N, N, N ′, N′-tetramethylchloroformamidinium chloride, N, N
N, N ', N'-tetraethyl chloroformamidinium chloride, N, N, N', N'-tetrabutyl chloroformamidinium chloride, N, N-diethyl-
N ′, N′-dipropylchloroformamidinium chloride, N, N-diethyl-N ′, N′-diallylchloroformamidinium chloride, N, N-diethyl-
N ', N'-dibutyl chloroformamidinium chloride, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-diethylimidazolinium chloride, 2-chloro-1,3-di Propyl imidazolinium chloride, 2-chloro-1,3-dibutyl imidazolinium chloride, 2-chloro-1,3
-Dihexylimidazolinium chloride, 2-chloro-1,3-dicyclohexylimidazolinium chloride, 2-chloro-1,3-diphenylimidazolinium chloride, 2-chloro-1,3-dimethyl-3,4,
Chlorides such as 5,6-tetrahydropyrimidinium chloride may be mentioned, but fluorides, bromides and iodides can be used in the same manner. These haloiminium salts can be used as a solid, or can be used without any problem even in a state of being dissolved or suspended in an appropriate solvent, and several haloiminium salts can be used in combination.

The amount of the haloiminium salt used in the present invention is such that the carboxyl group residual amount after the reaction is 0.2 mol% based on the total amount of the hydroxycarboxylic acid monomer units.
There is no problem if the stoichiometric amount is not less than the following stoichiometric amount, but preferably the stoichiometric amount is not less than the stoichiometric amount at which the residual amount of the carboxyl group is 0.1 mol% or less based on the total amount of the hydroxycarboxylic acid monomer units. When the residual amount of the carboxyl group is more than 0.2 mol% based on the total amount of the hydroxycarboxylic acid monomer units, the attained molecular weight decreases, and it becomes impossible to obtain a polymer having satisfactory mechanical properties.

During the course of the reaction, the formation of the polymer proceeds while the haloiminium salt releases hydrogen halide. Therefore, in order to obtain a high molecular weight polymer, it is necessary to remove hydrogen halide in the reaction system. As a method for removing hydrogen halide, a method of removing hydrogen halide gas by heating or a method of removing the halide from the system by using a base in the form of a salt is generally used. In the present invention, either of them may be used.

When a base is not used, the reaction temperature for obtaining the polymer depends on the kind of the haloiminium salt used and the kind of the starting hydroxycarboxylic acid and is not particularly limited, but is preferably from 40 to 200. It can be carried out sufficiently in the range of ° C. If the temperature exceeds 200 ° C., decomposition of the haloiminium salt itself tends to occur. If the temperature is lower than 40 ° C., the reaction rate is reduced, so that it is not a preferable temperature.
When a base is used, the reaction is preferably performed at 0 to 100 ° C.
Although the reaction at a temperature lower than 0 ° C. is possible, the reaction rate is slow, and it is necessary to carry out the reaction using a refrigerant or the like.
At a temperature exceeding 0 ° C., an impurity in which a hydroxyl group is substituted by a halogen (hereinafter abbreviated as a halogen-substituted product) due to halogenation of the terminal hydroxyl group at the stage of polymer chain growth and the terminal is blocked, so that the polymer is blocked. Is not a preferred method due to the low molecular weight of The reaction pressure can be freely selected and is not particularly limited.

In the present invention, the solvent used in the reaction varies depending on the skeletal structure and molecular weight of the target polymer, but it does not react with the haloiminium salt used and the reaction raw materials under the conditions during the reaction. When the solvent is distilled off by mixing with water, basically any one can be used as long as it has a lower boiling point than water or azeotropes with water. In selecting a solvent, ethylene dichloride, dichloromethane, chloroform, benzene, toluene, xylene, mesitylene, cumene, cymene, monochlorobenzene, o-dichlorobenzene and the like are selected, and particularly preferred are ethylene dichloride, dichloromethane, and chloroform. is there. One of these solvents may be used, or a plurality of solvents may be mixed and used.

In the present invention, pKa (the logarithm of the reciprocal of the acid dissociation constant) is defined as pKa measured at 25 ° C. in an aqueous solution.
a. When a base is used when polymerizing hydroxycarboxylic acid and / or its oligomer with a haloiminium salt, the pKa is not less than 4.9.
Secondary amines are used. Basically, there is no particular limitation as long as the tertiary amine has a pKa of 4.9 or more. Tertiary amines include, for example, quinoline, isoquinoline, N, N-dimethylpiperazine, N, N-diethylpiperazine, quinaldine, 2-ethylpyridine, β-picoline, 4-ethylpyridine, 3,5-lutidine, 6-lutidine, 4
-Methylmorpholine, 2,4,6-collidine and the like, but there is no particular limitation as long as it is a tertiary amine having a pKa of 4.9 or more and less than 8.0. A plurality of bases may be used simultaneously. When the base is used, a polyhydroxycarboxylic acid can be obtained in a relatively short time under relatively mild conditions. The amount of the base used is not particularly limited, but is preferably in the range of 2 to 10 moles, more preferably 2 to 3 moles, based on the haloiminium salt. If it is less than twice the mol of the haloiminium salt, the molecular weight of the polyhydroxycarboxylic acid cannot be sufficiently increased, and it is necessary to subsequently reach the desired molecular weight by thermal polymerization. Further, if the base exceeds 10 times the mol of the haloiminium salt, not only is it economically disadvantageous, but the base used at the time of isolating the polyhydroxycarboxylic acid easily remains in the polyhydroxycarboxylic acid,
At the same time, amides, ureas, and imidazolidinones generated after the reaction of the haloiminium salt tend to remain in the polyhydroxycarboxylic acid. When a polyhydroxycarboxylic acid is synthesized under such conditions, the bases, amides, ureas, and imidazolidinones used for the polyhydroxycarboxylic acid remain, but a large amount of water or a large amount of dilute aqueous sulfuric acid or dilute hydrochloric acid remains. Although it can be removed by washing or sludge with an acidic water such as water, use of an unnecessarily large amount of a base is not a preferable method from an economic viewpoint.

The atmosphere in the reaction system is preferably carried out under a flow of an inert gas such as nitrogen or argon in order to prevent the incorporation of moisture from outside the system. Or it can be carried out without problems even in a closed system.

A reaction solution containing the polyhydroxycarboxylic acid thus obtained and amides, ureas or imidazolidinones (when a base is used, a salt of the base with hydrogen halide is also included in the reaction solution). Is mixed with or mixed with a suspension of water and a solvent different from the reaction solvent, and then the polyhydroxycarboxylic acid is precipitated in water while distilling off the reaction solvent and the solvent different from the reaction solvent under normal pressure or reduced pressure The resulting mixture is subjected to solid-liquid separation and washed or sludged with water or an acidic water such as a dilute hydrochloric acid solution or a dilute sulfuric acid solution, so that a polyhydroxycarboxylic acid can be isolated in a satisfactory yield, quality and productivity. Depending on the type of polymer, molecular weight, type of solvent, and removal conditions, polyhydroxycarboxylic acid precipitates as relatively large particles, so amides, ureas, and imidazolidinones may remain in the polyhydroxycarboxylic acid. In that case, the reaction solvent is distilled off and precipitated while being pulverized using a pulverizer.Or, after polyhydroxycarboxylic acid is precipitated in a granular form, pulverized and separated into solid and liquid to separate water or diluted hydrochloric acid, diluted sulfuric acid. By washing or sludge with acidic water such as water, it is possible to isolate polyhydroxycarboxylic acid in terms of yield, quality and productivity.

In the present invention, the solvent different from the reaction solvent is not particularly limited as long as it is lower than the boiling point of water or azeotropic with water. Preferably, toluene, xylene, mesitylene and monochlorobenzene are used. But,
Particularly preferred are toluene, xylene and mesitylene.

The mixing temperature of the reaction solution and the suspension of water and a solvent different from the reaction solvent is not particularly limited.
１００100 ° C. It may be performed at a temperature lower than 0 ° C by dissolving salts etc. in water to lower the freezing point, but when distilling off the reaction solvent, the reaction solvent adheres easily to the water or polymer and tends to remain, and cooling with a refrigerant is necessary This is not a preferable method from an economic viewpoint. When used at a temperature higher than 100 ° C., the molecular weight may be significantly reduced due to hydrolysis of the polyhydroxycarboxylic acid, but if this does not occur, it is possible to carry out the operation at a higher water temperature. The amount of water used is not particularly limited, but is 2 to 20% by weight with respect to the polymer in consideration of the liquidity (operability) of mixing the reaction solution, evaporating the solvent, and depositing the polyhydroxycarboxylic acid. It is preferable to use twice as much water
If the weight is less than the weight, the operability of stirring, liquid transfer, etc. is poor.
When used more than twice the weight, there is no particular problem, but it is not a preferable method because the volume efficiency is reduced and the productivity is reduced. The method of solid-liquid separation can be generally performed by filtration, centrifugation, decantation, etc., but the solid-liquid separation method is not particularly limited in the present invention. The reaction solution containing polyhydroxycarboxylic acid and amides, ureas or imidazolidinones (in the case of using a base, a salt of the base with hydrogen halide is also included in the reaction solution) contains a dispersant. Mixed with water,
While dispersing or after mixing and dispersing, polyhydroxycarboxylic acid is precipitated in water while distilling off the reaction solvent under normal pressure or reduced pressure, solid-liquid separated, and washed with water or an acidic water such as a dilute hydrochloric acid aqueous solution or a dilute sulfuric acid aqueous solution. Alternatively, polyhydroxycarboxylic acid can be isolated by sludge and solid-liquid separation. Examples of the dispersant include ionic surfactants such as carboxylic acid metal salts, sulfonic acid metal salts, phosphonic acid metal salts, and nonionic surfactants such as polyols and polyoxyalkylene ether surfactants. Can be used as a dispersant.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to only the examples. In addition, 1,3-dimethylimidazolidinone (abbreviated as DMi) and β-picoline described in Examples are analyzed by gas chromatography. The weight average molecular weight (in terms of polystyrene) is as follows:
GPC system-11 (manufactured by Showa Denko KK) was used at 40 ° C. in a chloroform solvent.

EXAMPLE 1 200.0 g (2.00%) of 90% L-lactic acid (manufactured by ADM)
mol) was charged into a flask equipped with a 300 ml capillary, and nitrogen was blown from the capillary to 90-1.
Dehydration and removal of low-boiling-point impurities were conducted at 100 to 50 mmHg for 5 hours under reduced pressure at 20 ° C.
1 l with stirrer and Dean stack reflux
Transfer to a flask and add 1,2-dichloroethane (hereinafter referred to as EDC
14.4 g). The reaction solution was subjected to azeotropic dehydration under reflux of EDC to 160 ° C. and normal pressure to obtain 1 reaction solution.
When the temperature exceeded 60 ° C., the temperature was raised to 160 ° C. and the operation was continued for 6 hours while dropping the EDC using EDC as a temperature regulator to obtain an EDC solution of a lactic acid oligomer. As a result, the amount of EDC used as a temperature regulator was 20 g. The EDC solution of the lactic acid oligomer was cooled to 50 ° C., and 144 g of dehydrated EDC was further charged. Degree of polymerization of lactic acid oligomer in EDC solution of lactic acid oligomer n = 11.2
It was 0. While maintaining the temperature of 50 ° C., the EDC solution of the lactic acid oligomer was charged with 40.2 g of β-picoline,
Thereafter, 35.3 g of 2-chloro-1,3-dimethylimidazolinium chloride having a purity of 94% was charged all at once, and 6
Polymerized for hours. 227.1 g of dehydrated EDC was added to the polymerization reaction solution.
Was diluted. The polymerization reaction solution was transferred to a dropping funnel, and 5
The temperature was kept at 0 ° C., and 42 liters of water was added to the 1-liter flask equipped with the dropping funnel, the stirrer and the Dean stack reflux device.
While 3.8 g and 302.73 g of xylene were charged and heated and maintained at 50 ° C., the polymerization reaction solution was dropped from a dropping funnel into water / xylene in a 1 liter flask adjusted to a reduced pressure of 180 mmHg. EDC / xylene was azeotropically distilled out of the system as the dropping proceeded, and the entire amount of the reaction solution was charged 6 hours after the start of the dropping while returning the azeotropic water to the system. On the other hand, under reduced pressure conditions, the pressure was gradually adjusted during the dropping of the polymerization mass, and finally adjusted to 60 mmHg. It was confirmed that the distillation of EDC was completed and the distillation of xylene stopped. By this operation, an aqueous slurry of polylactic acid was obtained. The slurry was filtered at 50 ° C., washed with warm water at 50 ° C., and the wetted polylactic acid was further washed with water 272.
The mixture was sludged at 50 ° C. for 1 hour in 5 g, filtered and washed to obtain a wet polylactic acid. The contents of DMi and β-picoline in the wet body were both 50 ppm or less. The wet body was dried to isolate 140.4 g of polylactic acid at a yield of 97.5%. It was confirmed that the contents of DMi and β-picoline in the polylactic acid after isolation were also 50 ppm or less. The weight average molecular weight of the isolated polylactic acid is 120,000.
Met.

Example 2 200.0 g (2.00%) of 90% L-lactic acid (manufactured by ADM)
mol) was charged into a flask equipped with a 300 ml capillary, and nitrogen was blown from the capillary to 90-1.
Dehydration and removal of low boiling point impurities were performed at 20 ° C. under reduced pressure at 100 to 50 mmHg for 5 hours, and 162.0 g of the reaction solution was transferred to a 1-liter flask equipped with a stirrer and a Dean stack recirculator, and 14.4 g of monochlorobenzene was charged. did. The reaction solution was refluxed with monochlorobenzene at 〜160 ° C.
If the reaction liquid exceeds 160 ° C. under normal pressure and the reaction liquid exceeds 160 ° C., the operation is continued at 160 ° C. for 6 hours while dropping the monochlorobenzene using the monochlorobenzene as a temperature adjuster, and the operation is continued for 6 hours. A chlorobenzene solution was obtained. As a result, the amount of monochlorobenzene used as the temperature regulator was 50 g. The monochlorobenzene solution of the lactic acid oligomer was cooled to 100 ° C., and 450.4 g of dehydrated monochlorobenzene was further charged. The degree of polymerization of the lactic acid oligomer in the monochlorobenzene solution of the lactic acid oligomer was n = 10.90. While maintaining the temperature of 100 ° C., the monochlorobenzene solution of the lactic acid oligomer was charged with 40.2 g of β-picoline, and then 35.3 g of 2-chloro-1,3-dimethylimidazolinium chloride having a purity of 94%. Was charged all at once and polymerized for 4 hours. 229.9 dehydrated monochlorobenzene was added to the polymerization reaction solution.
g was charged and diluted. The polymerization reaction solution was transferred to a dropping funnel and kept at 100 ° C., and 423.8 g of water and 302.73 g of xylene were charged into a 1-liter flask equipped with the dropping funnel, a stirrer, and a Dean stack reflux device. 50 ℃
The polymerization reaction solution was dropped from a dropping funnel into water / xylene in a 1 liter flask adjusted to a reduced pressure of 180 mmHg, and only monochlorobenzene was initially distilled off from the system. Both xylene and xylene were distilled out of the system by azeotropic distillation, and the entire amount of the reaction solution was charged in 6 hours from the start of dropping while returning the azeotropic water into the system. On the other hand, under reduced pressure conditions, the pressure was gradually adjusted during the dropping of the polymerization mass, and finally adjusted to 60 mmHg. It was confirmed that distillation of monochlorobenzene was completed and distillation of xylene stopped. By this operation, an aqueous slurry of polylactic acid was obtained. The slurry was filtered at 50 ° C., washed with warm water at 50 ° C., and the wet polylactic acid was further sludge-filtered at 27 ° C. for 1 hour in 272.5 g of water at 50 ° C., filtered and washed to remove the wet polylactic acid. Obtained. The contents of DMi and β-picoline in the wet body were both 50 ppm or less. The wet body was dried to isolate 140.8 g of polylactic acid having a yield of 97.8%. It was confirmed that the contents of DMi and β-picoline in the polylactic acid after isolation were also 50 ppm or less. The weight average molecular weight of the isolated polylactic acid was 136,000.

Example 3 200.0 g (2.00%) of 90% L-lactic acid (manufactured by ADM)
mol) was charged into a flask equipped with a 300 ml capillary, and nitrogen was blown from the capillary to 90-1.
Dehydration and removal of low boiling point impurities were performed at 20 ° C. under reduced pressure at 100 to 50 mmHg for 5 hours, and 162.0 g of the reaction solution was transferred to a 1-liter flask equipped with a stirrer and a Dean stack recirculator, and 14.4 g of monochlorobenzene was charged. did. The reaction solution was refluxed with monochlorobenzene at 〜160 ° C.
When the reaction solution exceeds 160 ° C. under azeotropic dehydration at normal pressure, the operation is continued at 160 ° C. for 6 hours while dropping the monochlorobenzene using monochlorobenzene as a temperature regulator, and the operation is continued for 6 hours to obtain monochlorobenzene of lactic acid oligomer. A solution was obtained. As a result, the amount of monochlorobenzene used as the temperature regulator was 50 g. The monochlorobenzene solution of the lactic acid oligomer was cooled to 100 ° C., and 450.4 g of dehydrated monochlorobenzene was further charged. The degree of polymerization of the lactic acid oligomer in the monochlorobenzene solution of the lactic acid oligomer was n = 11.00. The monochlorobenzene solution of the lactic acid oligomer was kept at 140 ° C. for 2-
Chloro-1,3-dimethylimidazolinium chloride (35.3 g) was charged all at once, and polymerization was carried out for 15 hours while blowing in nitrogen. The polymerization reaction solution contains dehydrated monochlorobenzene 2
29.9 g were charged and diluted. The polymerization reaction solution was transferred to a dropping funnel and kept at 100 ° C., and 423.8 g of water and 302.73 g of xylene were charged into a 1-liter flask equipped with the dropping funnel, a stirrer, and a Dean stack reflux device. While maintaining the temperature at 50 ° C. and dropping the polymerization reaction solution from a dropping funnel into water / xylene in a 1 l flask adjusted to a reduced pressure of 180 mmHg, only monochlorobenzene was initially distilled out of the system, and as the addition proceeded, Both monochlorobenzene and xylene were distilled out of the system by azeotropic distillation, and the entire amount of the reaction solution was charged in 6 hours from the start of dropping while returning the azeotropic water to the system. On the other hand, under reduced pressure conditions, the pressure was gradually adjusted during the dropping of the polymerization mass, and finally adjusted to 60 mmHg. It was confirmed that distillation of monochlorobenzene was completed and distillation of xylene stopped. By this operation, an aqueous slurry of polylactic acid was obtained. The slurry was filtered at 50 ° C., washed with warm water at 50 ° C., and the wetted polylactic acid was further dried with 272.5 g of water.
The mixture was sludged at 50 ° C. for 1 hour, filtered and washed to obtain a wet polylactic acid. The content of DMi in the wet body was 50 ppm or less. The wet body was dried, and 139.7 g of polylactic acid was isolated at a yield of 97.0%. D in polylactic acid after isolation
It was confirmed that the content of Mi was also 50 ppm or less.
The weight average molecular weight of the isolated polylactic acid is 12,000
It was 0.

Example 4 200.0 g (2.00%) of 90% L-lactic acid (manufactured by ADM)
mol) was charged into a flask equipped with a 300 ml capillary, and nitrogen was blown from the capillary to 90-1.
Dehydration and removal of low-boiling-point impurities were performed at 100 to 50 mmHg for 5 hours under reduced pressure at 20 ° C., and 162.0 g of the reaction solution was transferred to a 1-liter flask equipped with a stirrer and a Dean stack recirculator, and 1,2-dichloroethane (hereinafter EDC) was added. 14.4 g). The reaction solution was refluxed under EDC.
The azeotropic dehydration was performed at 160 ° C. and normal pressure to obtain a reaction solution of 160 ° C.
When the temperature exceeds 100 ° C., EDC is used as a temperature regulator and the ED
The operation was continued for 6 hours at 160 ° C. while C was added dropwise to obtain an EDC solution of the lactic acid oligomer. As a result, the amount of EDC used as a temperature regulator was 20 g. The EDC solution of the lactic acid oligomer was cooled to 50 ° C., and 144 g of dehydrated EDC was further charged. ED of the lactic acid oligomer
The polymerization degree n of the lactic acid oligomer in the C solution was 11.20. While maintaining the temperature of 50 ° C., the EDC solution of the lactic acid oligomer was charged with 40.2 g of β-picoline, and then 35.3 g of 2-chloro-1,3-dimethylimidazolinium chloride having a purity of 94% was added. It was charged all at once and polymerized for 6 hours. 227.1 g of dehydrated EDC was charged and diluted in the polymerization reaction solution. The polymerization reaction solution was transferred to a dropping funnel and kept at 50 ° C.
423. Water was added to a 1-liter flask equipped with the dropping funnel, stirrer, and Dean stack reflux device.
8 g and monochlorobenzene 302.73 g are charged and 50
C., and while the polymerization reaction solution was dropped from a dropping funnel into water / monochlorobenzene in a 1 l flask adjusted to a reduced pressure of 180 mmHg from the dropping funnel, only EDC was initially distilled out of the system. Both the monochlorobenzene and the monochlorobenzene were distilled out of the system by azeotropic distillation, and the entire amount of the reaction solution was charged in 6 hours from the start of the dropwise addition while returning the azeotropic water to the system. On the other hand, under reduced pressure conditions, the pressure was gradually adjusted during the dropping of the polymerization mass, and finally adjusted to 60 mmHg. It was confirmed that the distillation of EDC was completed and the distillation of monochlorobenzene was stopped. By this operation, an aqueous slurry of polylactic acid was obtained. The slurry was filtered at 50 ° C and washed with warm water at 50 ° C,
Further, the wet body of the polylactic acid was dissolved in 272.5 g of water for 50 minutes.
C., sludge for 1 hour, filtration and washing to obtain a wet body of polylactic acid. The contents of DMi and β-picoline in the wet body were both 200 ppm. The wet body is dried to obtain a yield of 98.
141.1 g of polylactic acid was isolated at 0%. The content of DMi and β-picoline in the polylactic acid after isolation was also 30.
It was confirmed that it was 0 ppm. The weight average molecular weight of the isolated polylactic acid was 120,000.

Example 5 90% L-lactic acid (manufactured by ADM) 200.0 g (2.00
mol) was charged into a flask equipped with a 300 ml capillary, and nitrogen was blown from the capillary to 90-1.
Dehydration and removal of low-boiling impurities were performed at 100 to 50 mmHg under reduced pressure at 20 ° C. for 5 hours. 14.4 g). The reaction solution was refluxed under EDC.
The azeotropic dehydration was performed at 160 ° C. and normal pressure to obtain a reaction solution of 160 ° C.
When the temperature exceeds 100 ° C., EDC is used as a temperature regulator and the ED
The operation was continued for 6 hours at 160 ° C. while C was added dropwise to obtain an EDC solution of the lactic acid oligomer. As a result, the amount of EDC used as a temperature regulator was 20 g. The EDC solution of the lactic acid oligomer was cooled to 50 ° C., and 144 g of dehydrated EDC was further charged. ED of the lactic acid oligomer
The polymerization degree n of the lactic acid oligomer in the C solution was 11.30. While maintaining the temperature of 50 ° C., the EDC solution of the lactic acid oligomer was charged with 40.2 g of β-picoline, and then 35.3 g of 2-chloro-1,3-dimethylimidazolinium chloride having a purity of 94% was added. It was charged all at once and polymerized for 6 hours. 227.1 g of dehydrated EDC was charged and diluted in the polymerization reaction solution. The polymerization reaction solution was transferred to a dropping funnel and kept at 50 ° C.
423. Water was added to a 1-liter flask equipped with the dropping funnel, stirrer, and Dean stack reflux device.
8 g and monochlorobenzene 302.73 g are charged and 50
C., and while the polymerization reaction solution was dropped from a dropping funnel into water / monochlorobenzene in a 1 l flask adjusted to a reduced pressure of 180 mmHg from the dropping funnel, only EDC was initially distilled out of the system. / Both monochlorobenzene were distilled out of the system by azeotropic distillation, and the entire amount of the reaction solution was charged in 6 hours from the start of the dropwise addition while returning the azeotropic water into the system. During the dropping, the content was decanted at an appropriate time, and the solid was taken out of a mortar and returned to the reactor while pulverizing. On the other hand, under reduced pressure conditions, the pressure was gradually adjusted while the polymerization mass was being dropped, and finally 6
It was adjusted to 0 mmHg. It was confirmed that the distillation of EDC was completed and the distillation of monochlorobenzene was stopped. By this operation, an aqueous slurry of polylactic acid was obtained. The slurry was filtered at 50 ° C., washed with warm water at 50 ° C., and the wet polylactic acid was further sludge-filtered at 27 ° C. for 1 hour in 272.5 g of water at 50 ° C., filtered and washed to remove the wet polylactic acid. Obtained. The contents of DMi and β-picoline in the wet body were both 70 pp
m. The wet body was dried, and 139.5 g of polylactic acid was isolated at a yield of 96.9%. D in polylactic acid after isolation
It was confirmed that the contents of Mi and β-picoline were also 100 ppm. The weight average molecular weight of the isolated polylactic acid was 130,000.

Reference Example Polylactic acid not containing DMi and β-picoline (hereinafter abbreviated as purified polylactic acid) was formed into pellets. 100 ppm, 500 ppm, and 10 ppm DMi in purified polylactic acid
00 ppm was added and molded into a pellet. β-picoline was also added to purified polylactic acid at 500 ppm and molded into pellets. In addition, both DMi and β-picoline
The mixture was added in an amount of 0 ppm and formed into a pellet. The same molding machine was used. After molding all the samples into a sheet under the same conditions using the pellets, the YI value was measured. The results are described below.

[0027]

[Table 1] The larger the YI value of the sheet, the greater the coloring.

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Industrial Applicability The present invention provides a method for polymerizing a hydroxycarboxylic acid and / or an oligomer thereof using a haloiminium salt and isolating the resulting polyhydroxycarboxylic acid in a satisfactory form in terms of quality and productivity. And contributes to an efficient method for producing polyhydroxycarboxylic acid.

Claims (3)

[Claims] 1. A reaction system comprising a hydroxycarboxylic acid and / or
Alternatively, a reaction solution of polyhydroxycarboxylic acid obtained by allowing a haloiminium salt to act on a solution of the oligomer, a solvent different from the reaction solvent, and dropwise or after dropping into a suspension with water Isolating the polyhydroxycarboxylic acid by distilling off a solvent different from the reaction solvent and the reaction solvent and precipitating the polyhydroxycarboxylic acid in water, and then subjecting the slurry liquid to solid-liquid separation. For isolating a polyhydroxycarboxylic acid. 2. Hydroxycarboxylic acid and / or a reaction solvent.
Alternatively, a reaction solution of a polyhydroxycarboxylic acid obtained by reacting a solution of the oligomer with a hydroxycarboxylic acid and / or a haloiminium salt on the oligomer is mixed with a suspension of water and a solvent different from the reaction solvent. While dripping into or after dropping, the reaction solvent and the reaction solvent are pulverized while distilling off a different solvent and polyhydroxycarboxylic acid is precipitated in water, and then the slurry liquid is subjected to solid-liquid separation, A method for isolating a polyhydroxycarboxylic acid, comprising isolating the polyhydroxycarboxylic acid. 3. The method for isolating a polyhydroxycarboxylic acid according to claim 1, wherein the reaction solvent and the solvent different from the reaction solvent have a lower boiling point than water or are azeotropic with water.